JP2008094803A - Photosensitive resin composition and its laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having excellent sensitivity and resolution of a resist pattern after development, generating little scum in a developing stage, having excellent contrast after exposure, forming peeled pieces having small sizes, giving a cured film having excellent softness and useful as a DFR for the preparation of a substrate for an alkali-developing printed circuit board, a lead frame and a semiconductor package. <P>SOLUTION: The photosensitive resin composition contains (a) 20-90 mass% binder resin composed of a linear polymer having a carboxy group content of 100-600 in terms of an acid equivalent and a weight-average molecular weight of 20,000-500,000, (b) 5-75 mass% photopolymerizable monomer having at least one terminal ethylenic unsaturated group and (c) 0.01-30 mass% photopolymerization initiator containing a specific compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition and a photosensitive resin laminate, and in particular, can be alkali-developable suitable for producing printed wiring boards, lead frames, semiconductor package substrates, uneven substrates obtained through a sandblasting process, and the like. The present invention relates to a photosensitive resin composition and a photosensitive resin laminate.

Conventionally, as a resist for producing a printed wiring board, a lead frame and a semiconductor package substrate, a concavo-convex substrate obtained through a sandblasting process, a so-called dry film resist (hereinafter, referred to as a required film) including a support layer and a photosensitive resin layer as essential layers. DFR may be abbreviated as DFR). The DFR is generally prepared by laminating a photosensitive resin layer made of a photosensitive resin composition on a support layer which is a support layer, and in many cases, further laminating a protective layer on the photosensitive resin layer. As the photosensitive resin composition used, an alkali developing type using a weak alkaline aqueous solution as a developing solution is generally used.
In order to produce a printed wiring board using DFR, the following methods are generally used. First, if there is a protective layer, peel it off and use a laminator or the like to place the photosensitive resin layer and the support layer on the permanent circuit creation substrate such as a copper clad laminate, and the photosensitive resin layer on the substrate side. Lamination is performed so as to adhere to each other, exposure is performed through a mask film of a wiring pattern, the support layer is peeled off as necessary, and the photosensitive resin layer in an unexposed portion is dissolved or dispersed and removed with a developer, and light is applied to the substrate. A resist pattern formed by curing is formed. Next, using the formed resist pattern as a mask, the metal surface of the substrate is treated by etching or plating, and the resist pattern is peeled off using an alkaline aqueous solution stronger than the developer to form a printed wiring board, etc. It is a method to do.

Recently, a so-called tenting method, in which through holes (through holes) are covered with a hardened resist and then etched, is often used because of the simplicity of the process. For the etching, cupric chloride, ferric chloride, a copper ammonia complex solution, or the like is used.
With the recent miniaturization of the printed wiring board circuit, high resolution of the resist pattern is required. From the viewpoint of productivity, it is required to improve the sensitivity of the photosensitive resin composition in order to shorten the exposure time. .
High resolution and high sensitivity are achieved by improving the crosslinking density of the photopolymerizable monomer contained in the photosensitive resin composition, but when the crosslinking density is improved, the cured film after photocuring tends to be hard and brittle. .

Exposure methods are diversified depending on the application. In recent years, maskless exposure that does not require a photomask called direct drawing by laser (hereinafter referred to as “direct drawing exposure”) has been rapidly spreading in recent years. As a light source for maskless exposure, light having a wavelength of 350 to 410 nm, particularly i-line or h-line (405 nm) is often used. By introducing this direct drawing method, it is possible to greatly reduce the cost represented by the total elimination of mask costs. Further, the yield can be greatly improved by improving the mask position accuracy with respect to the expansion and contraction of the substrate and by automating the exposure operation. Since various circuit patterns can be formed only by digitally processing the mask data, the delivery time can be shortened.
In response to the demand for high resolution of the resist pattern and improvement of the sensitivity of the photosensitive resin composition, 2- (ο-chlorophenyl) -4,5-diphenylimidazole dimer in the photosensitive resin composition It is known to be achieved by using as an initiator.

However, when development is performed using DFR using a photosensitive resin composition containing the initiator, the photopolymerization initiator has poor dispersion stability with respect to an alkaline developer, and the developer is used repeatedly. Therefore, when the dissolution ratio of the photosensitive resin composition in the unexposed portion with respect to the developer is increased, there is a problem that it tends to be generated as an aggregate (scum). When scum occurs, the scum adheres to the substrate after development, leading to a short circuit or disconnection defect. The frequency of cleaning the developing tank for removing the scum also increases. Therefore, for the purpose of reducing aggregates, (b) an attempt to use an alkylphenol type monofunctional monomer having good developer dispersibility as a photopolymerizable unsaturated compound (Patent Document 1) or a phenoxy type functional monomer is used. Although there was an attempt (Patent Document 2), none of them was satisfactory.
Further, Patent Document 3 discloses at least one hexaarylbiimidazole compound having at least one hydrophilic group, which treats a photopolymerizable composition that has little sludge accumulation and can be peeled off in water. A method is described. However, as shown in the comparative example of the present application, there is a problem that the cured film of the resist after photocuring lacks flexibility.

Patent Document 4 contains arylbisimitazole having at least one ethylenically unsaturated double bond in the molecule, and one ethylenically unsaturated double bond and one or more hydrophilic groups in the molecule. There is a disclosure of a polymer initiator having a structure obtained by copolymerization with a compound to be developed, and a photosensitive resin composition with little development aggregate is disclosed.
Thus, there is a need for a photosensitive resin composition that is excellent in developer dispersion stability in the development process and does not generate aggregates.
In addition, the determination by the defect inspection machine after the exposure is generally performed by discriminating the contrast between the unexposed part and the exposed part, and the photosensitive resin layer immediately after the exposure has a good contrast in order to improve productivity. It is required to have.
Moreover, when the peeling shape is large, there arises a problem that it is entangled with the transport roll of the peeling machine in the peeling process.

JP 2001-174986 A JP 2001-305730 A Japanese Patent No. 3479510 Japanese Patent Laid-Open No. 2006-232929

  The problems of the present invention are excellent in sensitivity, high resolution, little occurrence of scum in the development process, excellent contrast between the unexposed part after exposure and the exposed part, and the resist strip is small, It is to provide a photosensitive resin composition having excellent cured film flexibility.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a photosensitive resin composition containing a specific compound as a photopolymerization initiator. It came to complete.
That is, the present invention is as follows.
1. A compound represented by the following general formula (I):

（Ｘは水素又は炭素数１〜６の炭化水素基、Ｙ及びＺは、それぞれ独立にハロゲン基、炭素数１〜６の炭化水素基、アルコキシ基、及びヒドロキシル基からなる群より選ばれる一種の基であり、ｎ_１は１〜１０の整数、ｍ_１は１〜５の整数、ｍ_２及びｍ_３はそれぞれ独立に０〜５の整数である。）

(X is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, Y and Z are each independently selected from the group consisting of a halogen group, a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, and a hydroxyl group. And n ₁ is an integer of ₁ to 10, m ₁ is an integer of ₁ to 5, and m ₂ and m ₃ are each independently an integer of 0 to 5.)

（Ｘは水素又は炭素数１〜６の炭化水素基、Ｙ及びＺは、それぞれ独立に、ハロゲン基、炭素数１〜６の炭化水素基、アルコキシ基、及びヒドロキシル基からなる群より選ばれる一種の基であり、ｎ_１は１〜１０の整数、ｍ_１は１〜５の整数、ｍ_２及びｍ_３は０〜５の整数である。） 2. (A) Resin for binders comprising a linear polymer having a carboxyl group content of 100 to 600 in terms of acid equivalent and a weight average molecular weight of 5,000 to 500,000 with respect to the entire photosensitive resin composition: 20 -90 mass%, (b) photopolymerizable monomer having at least one terminal ethylenically unsaturated group: 5-75 mass%, (c) photopolymerization initiator: 0.01-30 mass%, c) A photosensitive resin composition comprising the following general formula (I) as a photopolymerizable initiator:

(X is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and Y and Z are each independently selected from the group consisting of a halogen group, a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, and a hydroxyl group. And n ₁ is an integer of ₁ to 10, m ₁ is an integer of ₁ to 5, m ₂ and m ₃ are integers of 0 to 5.)

（Ｌは、炭素数１〜６の炭化水素基又はアルコキシ基、ヒドロキシル基、及びハロゲン基からなる群より選ばれる一種の基であり、ｐは０〜５の整数である。） 3. (A) The binder resin contains at least one compound selected from the group represented by the following general formula (II) and general formula (III) as a copolymerization component. The photosensitive resin composition according to the description,

(L is a kind of group chosen from the group which consists of a C1-C6 hydrocarbon group or an alkoxy group, a hydroxyl group, and a halogen group, and p is an integer of 0-5.)

（Ｒ_０は水素原子又はメチル基、Ｍは、炭素数１〜６の炭化水素基又はアルコキシ基、ヒドロキシル基、及びハロゲン基からなる群より選ばれる一種の基であり、ｑは０〜５の整数である。）

(R ₀ is a hydrogen atom or a methyl group, M is a kind of group selected from the group consisting of a hydrocarbon group having 1 to 6 carbon atoms or an alkoxy group, a hydroxyl group, and a halogen group, and q is 0-5. (It is an integer.)

（Ｒ_３及びＲ_４は、それぞれ独立に、水素原子又はメチル基である。また、Ｒ_１及びＲ_２は、炭素数２〜６のアルキレン基であり、それぞれ同一であっても異なっていてもよく、異なっている場合、−（Ｒ_１−Ｏ）−及び−（Ｒ_２−Ｏ）−の繰り返し単位は、ブロック構造でもランダム構造でもよい。ｎ_２、ｎ_３、ｎ_４及びｎ_５は、０又は正の整数であり、これらの合計は２〜４０である。） 4). (B) The photopolymerizable monomer contains at least one compound selected from the group represented by the following general formulas (IV), (V), (VI) and (VII): Or 3. The photosensitive resin composition according to the description,

(R ₃ and R ₄ are each independently a hydrogen atom or a methyl group. R ₁ and R ₂ are each an alkylene group having 2 to 6 carbon atoms, which may be the same or different. If they are different, the repeating unit of-(R ₁ -O)-and-(R ₂ -O)-may be a block structure or a random structure, and n ₂ , n _3, n ₄ and n ₅ are 0 or a positive integer, the sum of which is 2-40.)

（Ｒ_７及びＲ_８は、それぞれ独立に、水素原子又はメチル基である。Ｒ_５及びＲ_６は炭素数２〜６のアルキレン基を示し、これらは同一であっても相違していてもよく、異なっている場合、−（Ｒ_５−Ｏ）−及び−（Ｒ_６−Ｏ）−の繰り返し単位は、ブロック構造でもランダム構造でもよい。ｎ_６、ｎ_７、ｎ_８及びｎ_９は、０又は正の整数であり、これらの合計は２〜４０である。）

(R ₇ and R ₈ are each independently a hydrogen atom or a methyl group. R ₅ and R ₆ represent an alkylene group having 2 to ₆ carbon atoms, which may be the same or different. When different, the repeating unit of-(R ₅ -O)-and-(R ₆ -O)-may be a block structure or a random structure, and n ₆ , n _7, n ₈ and n ₉ are 0 Or a positive integer, the sum of which is 2-40.)

（Ｒ_９及びＲ_１０はそれぞれ独立に水素原子又はメチル基であり、ｎ_１０，ｎ_１１及びｎ_１２は、それぞれ３〜１５の整数である。）

(R ₉ and R ₁₀ are each independently a hydrogen atom or a methyl group, and n ₁₀ , n _11, and n ₁₂ are each an integer of 3 to 15)

（Ｒ_１１は炭素数４〜１２の２価の有機基、Ｒ_１２、Ｒ_１３は水素またはメチル基を表す。また、Ａ及びＢは、炭素数２〜６のアルキレン基であり、それぞれ同一であっても異なっていてもよく、異なっている場合、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位は、ブロック構造でもランダム構造でもよい。ｍ_５、ｍ_６、ｍ_７及びｍ_８は、０又は正の整数であり、これらの合計は２〜４０である。）

(R ₁₁ represents a divalent organic group having 4 to 12 carbon atoms, R ₁₂ and R ₁₃ represent hydrogen or a methyl group. A and B are alkylene groups having 2 to 6 carbon atoms, which are the same as each other. In the case where they are different, the repeating unit of-(AO)-and-(BO)-may be a block structure or a random structure, m ₅ , m _6, m _7. And m ₈ is 0 or a positive integer, and the sum of these is 2 to 40.)

5. 2. ~ 4. A photosensitive resin laminate in which a photosensitive resin layer comprising the photosensitive resin composition according to any one of the above is provided on a support layer;
6). 4. on the substrate. A method of forming a resist pattern including a lamination step of forming a photosensitive resin layer using the photosensitive resin laminate described above, an exposure step, and a development step;
7). In the exposure step, direct drawing and exposure are performed. A resist pattern forming method according to claim 1,
8). 6. above. Or 7. A method for producing a printed wiring board comprising a step of etching or plating a substrate on which a resist pattern is formed by the method described above,
9. 6. above. Or 7. A method for producing a lead frame, comprising a step of etching a substrate on which a resist pattern is formed by the method described in 1.
10. 6. above. Or 7. A method of manufacturing a semiconductor package, including a step of etching or plating a substrate on which a resist pattern is formed by the method described in 1.
11. 6. above. Or 7. A method in which a substrate on which a resist pattern is formed by the method described in 1. is processed by a sandblasting process.

The photosensitive resin composition of the present invention has excellent sensitivity, high resolution, little occurrence of scum by the development process, excellent contrast between the unexposed part after exposure and the exposed part, and a resist strip. Is small and has the effect of being excellent in the flexibility of the cured film.

Hereinafter, the present invention will be described in detail.
The amount of carboxyl groups contained in the linear polymer constituting the binder resin (a) used in the photosensitive resin composition of the present invention must be 100 to 600, preferably 200 to 400, in terms of acid equivalent. is there. An acid equivalent means the mass of the linear polymer which has a 1 equivalent carboxyl group in it. The carboxyl group in the linear polymer is necessary for imparting developability and releasability to the alkaline aqueous solution to the photosensitive resin composition. When the acid equivalent is less than 100, the development resistance is lowered, adversely affecting the resolution and adhesion, and when it exceeds 600, the developability and the peelability are lowered.

  (A) The molecular weight of the linear polymer constituting the binder resin is 5,000 to 500,000. When the molecular weight of the linear polymer exceeds 500,000, the developability decreases. When the molecular weight is less than 5,000, the tenting film strength decreases, and the edge fuse (excess of the photosensitive resin layer during storage) becomes remarkable. The molecular weight of the linear polymer is preferably 10,000 to 300,000 in order to achieve the effects of the present invention better. The acid equivalent is measured by the potentiometric titration method using Hiranuma automatic titrator (COM-555) and 0.1 mol / L sodium hydroxide. The weight average molecular weight was measured by gel permeation chromatography (GPC) manufactured by JASCO (pump: Gulliver, PU-1580 type, column: Shodex (KF-807, KF-806M, KF-806M, KF-802.5). It is calculated | required as a weight average molecular weight (polystyrene conversion) by 4 series, moving bed solvent: Tetrahydrofuran, a polystyrene standard sample (The calibration curve use by Showex STANDARD SM-105 Polystyrene by Showa Denko KK).

(A) The linear polymer constituting the binder resin is obtained by copolymerizing one or more monomers from the following two types of monomers.
The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, and the like. Among these, (meth) acrylic acid is particularly preferable.
The second monomer is non-acidic, has one polymerizable unsaturated group in the molecule, has various properties such as developability of the photosensitive resin layer, resistance to etching and plating processes, and flexibility of the cured film. Chosen to retain the characteristics of Examples of such compounds include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. , 2-hydroxypropyl (meth) acrylate, (meth) acrylonitrile, vinyl compounds having a phenyl group (for example, styrene derivatives such as styrene and methylstyrene) and benzyl (meth) acrylate. Among these, styrene and its derivatives represented by the following general formula (II) and benzyl (meth) acrylate and its derivatives represented by the following general formula (III) are particularly preferable from the viewpoint of high resolution.

（Ｌは、炭素数１〜６の炭化水素基又はアルコキシ基、ヒドロキシル基、及びハロゲン基からなる群より選ばれる一種の基であり、ｐは０〜５の整数である。）

(L is a kind of group chosen from the group which consists of a C1-C6 hydrocarbon group or an alkoxy group, a hydroxyl group, and a halogen group, and p is an integer of 0-5.)

（Ｒ_０は水素原子又はメチル基、Ｍは、炭素数１〜６の炭化水素基又はアルコキシ基、ヒドロキシル基、及びハロゲン基からなる群より選ばれる一種の基であり、ｑは０〜５の整数である。）

(R ₀ is a hydrogen atom or a methyl group, M is a kind of group selected from the group consisting of a hydrocarbon group having 1 to 6 carbon atoms or an alkoxy group, a hydroxyl group, and a halogen group, and q is 0-5. (It is an integer.)

The styrene represented by the general formula (II) and derivatives thereof are preferably contained in 3 to 85% by mass in the (a) thermoplastic copolymer. From the viewpoint of resolution, it is 3% by mass or more, and from the viewpoint of developability, it is 85% by mass or less.
The benzyl (meth) acrylate represented by the general formula (III) and derivatives thereof are preferably contained in the thermoplastic copolymer (3) to 85% by mass. From the viewpoint of resolution, it is 3% by mass or more, and from the viewpoint of developability, it is 85% by mass or less.
(A) The binder resin is obtained by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting the mixture of monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol. The synthesis is preferably carried out by superheated stirring. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization, and emulsion polymerization may be used in addition to solution polymerization.
(A) The ratio with respect to the whole photosensitive resin composition of resin for binders is the range of 20-90 mass%, Preferably it is 30-70 mass%. (A) When the ratio of the binder resin is less than 20% by mass or more than 90% by mass, the resist pattern formed by exposure and development has characteristics as a resist, such as tenting, etching, and the like. It does not have sufficient resistance in various plating processes.

The (b) photopolymerizable monomer used in the photosensitive resin composition of the present invention may be a compound having a photopolymerizable group at the terminal, such as 1,6-hexanediol di (meth) acrylate, 1 4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propanedi (meth) acrylate, glycerol tri ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol pen (Meth) acrylate, trimethylolpropane triglycidyl ether tertri (meth) acrylate, bisphenol A diglycidyl ether terdi (meth) acrylate, and β-hydroxypropyl-β ′-(acryloyloxy) propyl phthalate, phenoxypolyethyleneglycol -Luacrylate and the like.
(B) It is a preferred embodiment of the present invention that the photopolymerizable monomer contains at least one compound selected from the group consisting of (IV) to (VII) represented by the following general formula.

（Ｒ_３及びＲ_４は、それぞれ独立に、水素原子又はメチル基である。また、Ｒ_１及びＲ_２は、炭素数２〜６のアルキレン基であり、それぞれ同一であっても異なっていてもよく、異なっている場合、−（Ｒ_１−Ｏ）−及び−（Ｒ_２−Ｏ）−の繰り返し単位は、ブロック構造でもランダム構造でもよい。ｎ_２、ｎ_３、ｎ_４及びｎ_５は、０又は正の整数であり、これらの合計は２〜４０である。）

(R ₃ and R ₄ are each independently a hydrogen atom or a methyl group. R ₁ and R ₂ are each an alkylene group having 2 to 6 carbon atoms, which may be the same or different. If they are different, the repeating unit of-(R ₁ -O)-and-(R ₂ -O)-may be a block structure or a random structure, and n ₂ , n _3, n ₄ and n ₅ are 0 or a positive integer, the sum of which is 2-40.)

（Ｒ_７及びＲ_８は、それぞれ独立に、水素原子又はメチル基である。Ｒ_５及びＲ_６は炭素数２〜６のアルキレン基を示し、これらは同一であっても相違していてもよく、異なって
いる場合、−（Ｒ_５−Ｏ）−及び−（Ｒ_６−Ｏ）−の繰り返し単位は、ブロック構造でもランダム構造でもよい。ｎ_６、ｎ_７、ｎ_８及びｎ_９は、０又は正の整数であり、これらの合計は２〜４０である。）

(R ₇ and R ₈ are each independently a hydrogen atom or a methyl group. R ₅ and R ₆ represent an alkylene group having 2 to ₆ carbon atoms, which may be the same or different. When different, the repeating unit of-(R ₅ -O)-and-(R ₆ -O)-may be a block structure or a random structure, and n ₆ , n _7, n ₈ and n ₉ are 0 Or a positive integer, the sum of which is 2-40.)

In the compounds represented by the general formulas (IV) and (V), R ₁ and R ₂ , R ₅ and R ₆ are preferably ethylene groups or propylene groups. The lower limit of n ₂ + n ₃ + n ₄ + n ₅ or n ₆ + n ₇ + n ₈ + n ₉ is preferably 2 or more, and the upper limit is preferably 40 or less. If these values are less than 2, the flexibility and tenting properties of the cured film deteriorate, and if these values exceed 40, the effect on resolution is not sufficient.
Examples of the compound represented by the general formula (IV) include 2,2-bis {4- (p-acryloxypolyethoxy) cyclohexyl} propane or 2,2-bis {4- (methacryloxypolyethoxy) cyclohexyl}. The ethoxy group of propane is monoethoxy, diethoxy, triethoxy, tetraethoxy, pentaethoxy, hexaethoxy, heptaethoxy, octaethoxy, nonaethoxy, decaethoxy, undecaethoxy, dodecaethoxy, tridecaethoxy, tetradecaethoxy, pentadecaethoxy. In addition, a mixture of an ethylene group and a propylene group is also included in the alkylene group, and 2,2-bis {4- (acryloxypolyalkyleneoxy) cyclohexyl} propane or 2,2-bis {4- (methacryloxypolyalkylene) Oxy) cyclo Alkyleneoxy groups cyclohexyl} propane adducts of adducts and random structure of the block structure of the adduct and tetraethoxy and tetrapropyloxy adducts and random structure of the block structure of octa ethoxy and di propyloxy and the like. Among these, 2,2-bis {4- (methacryloxypentaethoxy) cyclohexyl} propane is most preferable.

  Specific examples of the compound represented by the general formula (V) include polyethylene glycol dimethacrylate (2,2-bis {4- (methacryloxydi) having an average of 2 moles of ethylene oxide added to both ends of bisphenol A. Ethoxy) phenyl} propane) (NK ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.) and diglycolate of polyethylene glycol (2,2-bis {4 -(Methacryloxypentaethoxy) phenyl} propane) (NK ester BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), poly having an average of 6 moles of ethylene oxide and an average of 2 moles of propylene oxide added to both ends of bisphenol A. Dimethacrylate of alkylene glycol There are dimethacrylate polyalkylene glycol obtained by adding each average 15 moles of ethylene oxide and average 2 moles of propylene oxide to both ends of bisphenol A.

（Ｒ_９及びＲ_１０はそれぞれ独立に水素原子又はメチル基であり、ｎ_１０，ｎ_１１及びｎ_１２は、それぞれ３〜１５の整数である。）

(R ₉ and R ₁₀ are each independently a hydrogen atom or a methyl group, and n ₁₀ , n _11, and n ₁₂ are each an integer of 3 to 15)

In the compound represented by the general formula (VI), when n ₁₀ , n ₁₁ and n ₁₂ are smaller than 3, respectively, the boiling point of the compound is lowered, the odor of the resist is increased, and the use is difficult. Become. When n ₁₀ , n _11, and n ₁₂ exceed 20, the concentration of the photoactive site per unit weight becomes low, so that practical sensitivity cannot be obtained.
Specific examples of the compound represented by the above general formula (VI) include, for example, glycol dimethacrylate obtained by adding an average of 3 moles of ethylene oxide to both ends of polypropylene glycol to which an average of 12 moles of propylene oxide is added. -G.

（Ｒ_１１は炭素数４〜１２の２価の有機基、Ｒ_１２、Ｒ_１３は水素またはメチル基を表す。また、Ａ及びＢは、炭素数２〜６のアルキレン基であり、それぞれ同一であっても異なっていてもよく、異なっている場合、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位は、ブロック構造でもランダム構造でもよい。ｍ_５、ｍ_６、ｍ_７及びｍ_８は、０又は正の整数であり、これらの合計は２〜４０である。）

(R ₁₁ represents a divalent organic group having 4 to 12 carbon atoms, R ₁₂ and R ₁₃ represent hydrogen or a methyl group. A and B are alkylene groups having 2 to 6 carbon atoms, which are the same as each other. In the case where they are different, the repeating unit of-(AO)-and-(BO)-may be a block structure or a random structure, m ₅ , m _6, m _7. And m ₈ is 0 or a positive integer, and the sum of these is 2 to 40.)

In the compound represented by the general formula (VII), R ₁₁ is preferably a hexamethylene group, a cyclohexyl group, or a trimethylhexamethylene group. A and B are preferably ethylene groups or propylene groups. When n ₁₃ and n ₁₄ each exceed ₁₅ , the concentration of the photoactive site per unit weight becomes low, so that practical sensitivity cannot be obtained.
Examples of the compound represented by the general formula (VII) include diisocyanates such as hexamethylene diisocyanate, tolylene diisocyanate, or 2,2,4, -trimethylhexamethylene diisocyanate. And urethane compounds of a compound having a hydroxyl group and a (meth) acryl group in one molecule (such as 2-hydroxypropyl acrylate and oligopropylene glycol monomethacrylate). Specifically, a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Nippon Yushi Co., Ltd., Bremer-PP1000), hexamethylene diisocyanate and oligoethylene glycol And a reaction product of hexamethylene diisocyanate and oligoethylene glycol oligopropylene glycol monomethacrylate.

(B) The ratio of the photopolymerizable unsaturated compound is in the range of 5 to 75% by mass with respect to the entire photosensitive resin composition. (B) If the ratio of the photopolymerizable unsaturated compound is less than 5% by mass, sufficient sensitivity cannot be obtained, and if it exceeds 75% by mass, the edge fuse becomes remarkable. Preferably it is 10-70 mass%, More preferably, it is 15-60 mass%.
The photopolymerization initiator (c) used in the photosensitive resin composition of the present invention contains a compound represented by the following general formula (I). The photopolymerization initiator is a compound that is activated by various actinic rays, such as ultraviolet rays, and starts polymerization.

（Ｘは水素又は炭素数１〜６の炭化水素基、Ｙ及びＺは、それぞれ独立に、ハロゲン基、炭素数１〜６の炭化水素基、アルコキシ基、及びヒドロキシル基からなる群より選ばれる一種の基であり、ｎ_１は１〜１０の整数、ｍ_１は１〜５の整数、ｍ_２及びｍ_３はそれぞれ独立に０〜５の整数である。）

(X is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and Y and Z are each independently selected from the group consisting of a halogen group, a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, and a hydroxyl group. And n ₁ is an integer of ₁ to 10, m ₁ is an integer of ₁ to 5, and m ₂ and m ₃ are each independently an integer of 0 to 5.)

Examples of the 2,4,5-triarylimidazole dimer represented by the general formula (I) include 2- (p-methoxytriethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (P-ethoxytriethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxytetraethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-ethoxytetraethoxyphenyl) Although there are -4,5-diphenylimidazole dimer, 2- (p-methoxytriethoxyphenyl) -4,5-diphenylimidazole dimer is particularly preferable.
It is preferable to use p-aminophenyl ketone in combination with the compound represented by the general formula (I). Examples of p-aminophenyl ketone include p-aminobenzophenone, p-butylaminophenone, and p-dimethylaminoacetophenone. , P-dimethylaminobenzophenone, pp′-bis (ethylamino) benzophenone, pp′-bis (dimethylamino) benzophenone [Michler's ketone], pp′-bis (diethylamino) benzophenone, pp′- And bis (dibutylamino) benzophenone.

  In addition to the compounds shown above, other photopolymerization initiators can be used in combination with the photosensitive resin composition of the present invention. Other photopolymerization initiators include, for example, quinones such as 2-ethylanthraquinone and 2-tert-butylanthraquinone, aromatic ketones such as benzophenone, benzoin ethers such as benzoin, benzoin methyl ether and benzoin ethyl ether, Examples thereof include benzyl dimethyl ketal and benzyl diethyl ketal. Acridines such as 9-phenylacridine, oximes such as 1-phenyl-1,2-propanedione-2-ο-benzoyloxime, 1-phenyl-1,2-propanedione-2- (ο-ethoxycarbonyl) oxime Esters may be used. Examples of the initiator used in combination include a combination of a thioxanthone such as thioxanthone, 2,4-diethylthioxanthone, and 2-chlorothioxanthone and a tertiary amine compound such as a dimethylaminobenzoic acid alkyl ester compound.

(C) The ratio of a photoinitiator is 0.01-30 mass% with respect to the whole photosensitive resin composition, Preferably it is 0.05-10 mass%. (C) When the ratio of the photopolymerization initiator exceeds 30% by mass, the active absorption rate of the photosensitive resin composition increases, and when used as a photosensitive laminate, it is caused by polymerization of the bottom portion of the photosensitive resin layer. Curing becomes insufficient, and if it is less than 0.01% by mass, sufficient sensitivity cannot be obtained.
It is preferable that the ratio of the said general formula (I) is 0.01-20 mass% with respect to the whole photosensitive resin composition, More preferably, it is 0.05-10 mass%. The proportion of the general formula (I) is preferably 20% by mass or less from the viewpoint of the active absorption rate of the photosensitive resin composition, and is preferably 0.01 mass or more from the viewpoint of sensitivity.

  In order to improve the thermal stability and storage stability of the photosensitive resin composition of the present invention, it is preferable to contain a radical polymerization inhibitor in the photosensitive resin composition. Examples of the radical polymerization inhibitor used include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, and 2,6-di-tert-butyl-p-crezo. -2,2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, And diphenylnitrosamine.

The photosensitive resin composition of the present invention may contain coloring substances such as dyes and pigments. Examples of the coloring material used include fuchsin, phthalocyanine green, olamine base, paramadienta, crystal violet, methyl orange, Nile Bull-2B, Victoria Bull-, Malachite Green, Basic Bull-20, Diamond Green. Or the like.
The photosensitive resin composition of the present invention may contain a coloring dye that develops color when irradiated with light. Examples of the coloring dye used include a combination of a leuco dye or a fluorane dye and a halogen compound. Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green], and the like. Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2, 3 -Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, triazine compounds and the like. Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine. Among such coloring dyes, a combination of tribromomethylphenylsulfone and a leuco dye or a combination of a triazine compound and a leuco dye is useful.

The photosensitive resin composition of the present invention may contain an additive such as a plasticizer. Examples of the additive used include phthalic acid esters such as diethyl phthalate and p-toluenesulfonamide.
The photosensitive resin composition of the present invention may contain a solvent in order to obtain a uniformly dissolved preparation. Examples of the solvent used include ketones typified by methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. It is preferable to prepare the solvent so that the viscosity of the preparation liquid of the photosensitive resin composition is 500 to 4000 mPa · sec at 25 ° C.

The photosensitive resin laminate of the present invention is prepared by coating the photosensitive resin composition on a support layer.
The support layer is preferably a transparent layer that transmits active light, such as polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer. Examples include a coalesced film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film, and these stretched films can also be used. A thinner support layer is more advantageous in terms of image formation and economy, but a thickness of 10 to 30 μm is common from the viewpoint of maintaining strength. Moreover, what is 5% or less is used as a haze.

A protective layer may be laminated on the surface opposite to the photosensitive resin layer laminated on the support layer, if necessary. An important characteristic of the protective layer is that the protective layer has a sufficiently small adhesion to the photosensitive resin layer and can be easily peeled off than the support layer. Examples of the protective layer used include a polyethylene film and a polypropylene film. The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm.
As a board | substrate which laminates | stacks the photosensitive resin laminated body which consists of a photosensitive resin composition, the board | substrate for printed wiring boards, a lead frame, a semiconductor package, etc. are mentioned.
Although the thickness of the photosensitive resin layer varies depending on the application, generally 1 to 100 μm is used for the production of a printed wiring board, preferably 5 to 50 μm, and the thinner the photosensitive resin layer, the higher the resolution. The film strength is improved as the photosensitive resin layer is thicker.
A process for producing a printed wiring board or the like using the photosensitive resin laminate is performed by a known technique, but will be briefly described below.

<Resist pattern formation method>
A resist pattern using the photosensitive resin laminate of the present invention can be formed by a process including a lamination process, an exposure process, and a development process. An example of a specific method is shown.
First, a lamination process is performed using a laminator. In the case where the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated on the substrate surface with a laminator. In this case, the photosensitive resin layer may be laminated only on one side of the substrate surface or on both sides. The heating temperature at this time is generally 40 to 160 ° C. Moreover, adhesion and chemical resistance are improved by performing the thermocompression bonding twice or more. At this time, for the crimping, a two-stage laminator having two rolls may be used, or it may be repeatedly crimped through the roll several times.

Next, an exposure process is performed using an exposure machine. If necessary, the support is peeled off and exposed to active light through a photomask. The exposure amount is determined from the light source illuminance and the exposure time. You may measure using a photometer.
In the exposure process, a maskless exposure method may be used. In maskless exposure, exposure is performed by directly drawing on a substrate without using a photomask. As the light source, a semiconductor laser having a wavelength of 350 to 410 nm, an ultrahigh pressure mercury lamp, or the like is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the light source illuminance and the moving speed of the substrate.

Next, a developing process is performed using a developing device. After the exposure, if there is a support on the photosensitive resin layer, it is removed if necessary, and then the unexposed portion is developed and removed using a developer of an alkaline aqueous solution to obtain a resist image. An aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ or the like is used as the alkaline aqueous solution. These are selected in accordance with the characteristics of the photosensitive resin layer, but a Na ₂ CO ₃ aqueous solution having a concentration of 0.2 to 2% by mass and 20 to 40 ° C. is generally used. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed.
Although a resist pattern is obtained by the above-mentioned process, a heating process at 100 to 300 ° C. can be further performed depending on the case. By carrying out this heating step, chemical resistance can be further improved. For heating, a heating furnace of a hot air, infrared ray, far infrared ray or the like is used.

<Method for manufacturing printed wiring board>
The method for producing a printed wiring board according to the present invention is performed through the following steps following the above-described resist pattern forming method using a copper-clad laminate or a flexible substrate as a substrate.
First, a conductor pattern is formed on the copper surface exposed by development using a known method such as an etching method or a plating method.
Thereafter, the resist pattern is peeled from the substrate with an aqueous solution having alkalinity stronger than that of the developer to obtain a desired printed wiring board. The alkaline aqueous solution for peeling (hereinafter also referred to as “peeling solution”) is not particularly limited, but an aqueous solution of NaOH or KOH at a concentration of 2 to 5% by mass, 40 to 70 ° C. is generally used. It is possible to add a small amount of a water-soluble solvent to the stripping solution.

<Lead frame manufacturing method>
The lead frame manufacturing method of the present invention is performed through the following steps following the above-described resist pattern forming method using a metal plate of copper, copper alloy, iron-based alloy or the like as a substrate.
First, a conductive pattern is formed by etching the substrate exposed by development.
Thereafter, the resist pattern is peeled off by a method similar to the method for manufacturing a printed wiring board described above to obtain a desired lead frame.

<Semiconductor package manufacturing method>
The method for producing a semiconductor package of the present invention is performed by performing the following steps following the above-described resist pattern forming method using a wafer on which a circuit as an LSI has been formed as a substrate.
A conductor pattern is formed by performing columnar plating such as copper or solder on the opening exposed by development.
Thereafter, the resist pattern is peeled by the same method as the above-described printed wiring board manufacturing method, and the thin metal layer other than the columnar plating is removed by etching to obtain a desired semiconductor package.

<Processing method by sandblasting>
When processing the substrate by the sandblasting method using the photosensitive resin laminate of the present invention as a dry film resist, the photosensitive resin laminate is laminated on the substrate in the same manner as described above, Exposure and development are performed. Further, a blasting material is sprayed from the formed resist pattern to be cut to a desired depth, and a resin part remaining on the base material is removed from the base material with an alkaline stripping solution, etc. A fine pattern can be processed. The blasting material used for the above-mentioned sandblasting process may be a known material, for example, fine particles of about 2 to 100 μm such as SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass, stainless steel and the like.

<Reference Example 1>
Synthesis of Triethyleneglycolylmethyl Tosylate (TGME Tosylate) In a 300 ml three-necked flask, NaOH (9.94 g, 0.249 mol) / 50 ml of H ₂ O, Triethylenegenelymomethylether (28.75 g, 0.175 ml, cooled to 0,175 g, 0.175 ml, 0.175 ml). While stirring, 50 ml of p-toluenesulfonyl chloride (30.85 g, 0.162 mol) / THF was added dropwise and stirred for 2 h (≦ 5 ° C.). Thereafter, the mixture was put in 150 ml of ice water, extracted twice with methylene chloride, washed twice with water and once with saturated brine, and then dried over MgSO ₄ overnight. Thereafter, the solvent was distilled off to obtain a yellow transparent liquid. This was identified by IR, ¹ H-NMR, FAB-MS.
IR was model number FT / IR-410 manufactured by JASCO Corporation (JASCO), and measurement was performed by the conditional NaC1 method.
¹ H-NMR was a model number 500 MHz JNM ECP-500 manufactured by JEOL Ltd. (JEOL), and measurement was performed using the condition solvents CDC13 _and TMS as internal standards.
FAB-MS was model number JMS-700 manufactured by JEOL Ltd. (JEOL), and measurement was performed by ionization in a conditional FAB mode.
IR (cm ⁻¹ ) (NaCl): 3033 (ν, ArC—H), 2878 (ν, O—CH ₂ —CH ₂ —O), 1357 (ν, SO ₂ ), 1177 (ν, SO ₂ ), 1098 (ν, C—O—C),
¹ H-NMR (500 MHz, Acetone-d6) δ (ppm): 2.47 (s, 3H), 3.28 (s, 3H), 3.45-3.68 (m, 10H), 4.16 (T, J = 7 Hz, 2H), 7.49 (d, J = 13 Hz, 2H), 7.82 (d, J = 13 Hz, 2H)
MS (FAB) m / z: 319 (MH ^<+> )

<Reference Example 2>
p- (Triethyleneglycolmonomethylether) Benzaldehyde (p- TGME benzaldehyde) Synthesis 200ml eggplant flask TGME Tosylate (20.0g, 62.8mmol), 4-hydroxybenzaldehyde (8.70g, 71.2mmol), K 2 CO 3 (11 8 g, 85.3 mmol), and 50 ml of toluene and 100 ml of DMF were added to the solvent and refluxed for 24 h. The reaction product was filtered and the filtrate was distilled off. Thereafter, SiO ₂ column (eluent ethyl acetate: hexane = 1: 1). Thereafter, the solvent was distilled off to obtain a yellow transparent liquid. This was identified by IR, ¹ H NMR, FAB-MS.
IR (cm ⁻¹ ) (NaCl): 3073 (ν, ArC—H), 2876 (ν, O—CH ₂ —CH ₂ —O), 1692 (ν, C═O), 1111 (ν, C—O) -C)
¹ H NMR (500 MHz, CDCl ₃ ) δ (ppm): 3.38 (s, 3H), 3.55 (t, J = 5 Hz, 2H), 3.65-3.75 (m, 6H), 3 .89 (t, J = 5 Hz, 2H), 4.22 (t, J = 5 Hz, 2H), 7.02 (d, J = 9 Hz, 2H), 7.83 (d, J = 9 Hz, 2H) , 9.88 (s, 1H)
MS (FAB) m / z: 269 (MH ^<+> )

<Reference Example 3>
Synthesis of (p-methoxytriethoxyphenyl) -4,5-diphenylimidazole Benzil (2.37 g, 11.3 mmol), p-TGMEbenzaldehyde (3.10 g, 11.6 mmol), ammonium acetate (7. 16 g, 92.9 mmol) was added, and 20 ml of acetic acid was added to the solvent and refluxed for 3 h. The solvent of the reaction mixture was distilled off and extracted three times with methylene chloride and water. The organic layer was dried over Na ₂ SO ₄ overnight, after which the solvent was distilled off and purified on a SiO ₂ column (eluent initially using chloroform and later using ethyl acetate). Thereafter, the solvent was distilled off, followed by vacuum drying overnight to obtain a yellowish white viscous solid. This was identified by IR, ¹ H NMR, FAB-MS.
_{^{IR (cm -1) (CCl 4}} ): 3266 (ν, N-H), 3058 (ν, ArC-H), 2876 (ν, O-CH 2 -CH 2 -O), 1097 (ν, C- OC)
¹ H NMR (500 MHz, Acetone-d6) δ (ppm): 3.28 (s, 3H), 3.47 (t, J = 5 Hz, 2H), 3.57-3.61 (m, 4H), 3.67 (t, J = 5 Hz, 2H), 3.84 (t, J = 5 Hz, 2H), 4.19 (t, J = 5 Hz, 2H), 7.04-7.05 (m, 2H) ), 7.28-7.36 (m, 6H), 7.59-7.60 (m, 4H), 8.05-8.07 (m, 2H)
MS (FAB) m / z: 459 (MH ^<+> )

<Example 1>
Synthesis of 2- (p-methoxytriethoxyphenyl) -4,5-diphenylimidazole dimer (p-methoxytriethoxyphenyl) -4,5-diphenylimidazole (3) obtained in Reference Example 3 in a 200 ml eggplant flask .38 g, 7.38 mmol) and dissolved in 50 ml of CH ₂ Cl ₂ , K ₃ [Fe (CN) ₆ ] (8.96 g, 24.9 mmol) was added, and NaOH / H ₂ O 8.9 g was added. / 50 ml was added and refluxed for 20 h. After the reaction, 50 ml of water was added for liquid separation. The organic layer was dried over Na ₂ SO ₄ overnight, after which the solvent was distilled off and purified on a SiO ₂ column (eluent ethyl acetate). Thereafter, the solvent was distilled off, followed by vacuum drying overnight to obtain a green viscous solid. This was identified by IR, 1H NMR, FAB-MS.
IR (cm ⁻¹ ) (CCl ₄ ): 3059 (ν, ArC—H), 2875 (ν, O—CH ₂ —CH ₂ —O), 1111 (ν, C—O—C)
¹ H NMR (500 MHz, Acetone-d6) δ (ppm): 2.80-2.84 (m, 6H), 3.44-4.33 (m, 24H), 6.53-8.44 (m , 28H) MS (FAB) m / z: 915 (MH ⁺ )

<Examples 2-9, Comparative Examples 1-3>
Each compound was uniformly dissolved at the composition ratio of each Example and Comparative Example shown in Table 1 to prepare a mixed solution of the photosensitive resin composition. The prepared mixed solution was uniformly applied to a polyethylene terephthalate film having a thickness of 20 μm using a bar coater and dried in a dryer at 95 ° C. for 4 minutes. At this time, the thickness of the photosensitive resin layer was 40 μm. A DFR was obtained by laminating a 25 μm polyethylene film on the surface of the photosensitive resin layer on which no polyethylene terephthalate film was laminated.
The DFR polyethylene film obtained by polishing the surface of a copper-clad laminate on which 35 μm rolled copper foil is laminated with a wet buffer (manufactured by 3M, Scotch Bright (registered trademark) # 600, 2 series). Then, the photosensitive resin layer was laminated on a copper clad laminate at 105 ° C. with a hot roll laminator to obtain a laminate.

The following evaluation was performed about the obtained laminated body.
(1) Sensitivity test
The laminated body laminated on the copper-clad laminate was exposed at 40 mJ / cm ² with a super high pressure mercury lamp (HMW-201KB, manufactured by Oak Manufacturing Co., Ltd.) through a 21 step step tablet made by Strafer. Subsequently, the polyethylene terephthalate support layer was peeled off, and then a 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed for about 45 seconds. The highest remaining film stage number of the obtained cured resist was defined as sensitivity.

(2) Resolution The laminated body laminated on the copper-clad laminate is passed through a mask film having a line and space of 1: 1 by an ultra-high pressure mercury lamp (Oak Manufacturing Co., Ltd., HMW-201KB) at 60 mJ / cm ² . Exposed. Subsequently, after peeling off the polyethylene terephthalate support layer, a 1% by mass aqueous sodium carbonate solution at 30 ° C. was sprayed for about 45 seconds. The minimum line width that can be separated of the obtained images was defined as the resolution, and the ranking was performed as follows.
A: 40 μm or less ○: Over 40 μm, 45 μm or less Δ: Over 45 μm, 50 μm or less X: Over 50 μm

(3) Development cohesion test (Development scum test)
While dissolving the photosensitive resin layer of 0.5 m ² / L unexposed in 30 μm 1% by weight sodium carbonate aqueous solution in terms of 50 μm film thickness, spraying 200 mL of the solution at a pressure of 0.2 MPa. The solution is circulated for 3 hours. Thereafter, the state of occurrence of aggregates (scum) in the tank was visually determined and ranked as follows.
○: There is no suspended matter on the liquid surface, and no aggregates (scum) are generated at the bottom of the tank after the solution is removed. Δ: Slightly solid agglomerates (scum) are observed on the liquid level and tank bottom.
X: Generation | occurrence | production of a large amount of solid aggregates (scum) is recognized by the liquid level and the tank bottom.

(4) Evaluation of exposure contrast 60 mJ / by using a photosensitive resin layer in an unexposed portion 15 minutes after laminating a laminate laminated on a copper clad laminate and an ultra-high pressure mercury lamp (Oak Manufacturing Co., Ltd., HMW-201KB). The color difference ΔE of the photosensitive resin layer in the exposed area after 30 seconds of exposure at cm ² was measured with a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., NF333 simple spectral color difference meter), and ranked as follows: .
A: The value of ΔE exceeds 15.
○: The value of ΔE exceeds 10 and is 15 or less.
Δ: The value of ΔE exceeds 2 and is 10 or less.
X: The value of ΔE is 2 or less.

(5) Evaluation of peeled piece size A laminate of 4.2 cm × 6 cm exposed to the entire surface of a laminate laminated on a copper-clad laminate with an ultrahigh pressure mercury lamp (Oak Manufacturing Co., Ltd., HMW-201KB) at 60 mJ / cm ^2. The plate was immersed in an aqueous caustic soda solution (50 ° C., 3 mass%), and the shape of the cured film (peeling piece size) peeled from the laminated plate was ranked as follows.
A: The peeled piece size is 5 mm square or less.
○: The peeled piece size exceeds 5 mm square and is 10 mm square or less.
X: The peeling piece size exceeds 10 mm square.

(6) Cured film flexibility test The entire surface of the laminate laminated on the copper clad laminate was exposed at 60 mJ / cm ² with an ultrahigh pressure mercury lamp (Oak Manufacturing Co., Ltd., HMW-201KB). Subsequently, after peeling off the polyethylene terephthalate support layer, a 1% by mass aqueous sodium carbonate solution at 30 ° C. was sprayed for about 45 seconds. Using the crosscut guidance disclosed in IS K4100, the cured film-adhered substrate obtained after development was made to go straight to a width of 1 mm with a cutter, cut with 10 cutters, and the tape was peeled off. The state where the cured film peeled at that time was ranked according to the rank shown below.
A: The cured film does not peel at all after the cellophane tape is peeled off.
○: A part of the cured film is peeled off after peeling off the tape.
Δ: About half of the cured film is peeled off after peeling off the tape.
X: The cured film is peeled off almost entirely after the cellophane tape is peeled off.
The above results are summarized in Table 1.

<Explanation of symbols in Table 1>
P-1: Methyl tilketone solution of ternary copolymer of methyl methacrylate 50 mass%, methacrylic acid 25 mass%, styrene 25 mass% (solid content concentration 35 mass%, weight average molecular weight 50,000, acid equivalent 344)
P-2: Methyl ethyl ketone solution of ternary copolymer of 65% by mass of methyl methacrylate, 25% by mass of methacrylic acid, and 10% by mass of butyl acrylate (solid content concentration 30% by mass, weight average molecular weight 120,000, acid equivalent 344)
P-3: Methyl ethyl ketone solution of ternary copolymer of 50% by mass of benzyl methacrylate, 30% by mass of methacrylic acid, and 20% by mass of styrene (solid content concentration 41% by mass, weight average molecular weight 55,000, acid equivalent 287)
M-1: Diglycolate of glycol obtained by adding 3 mol of ethylene oxide to both ends of polypropylene glycol to which 12 mol of propylene oxide was added on average

M-2: Polymethacrylate glycol with an average of 2 moles of propylene oxide added to both ends of bisphenol A and polyethylene glycol with an average of 6 moles of ethylene oxide added M-3: Hexamethylene diisocyanate Urethane compound with tripropylene glycol monomethacrylate M-4: (2,2-bis {4- (methacryloxypentaethoxy) cyclohexyl} propane M-5: 4-normalnonylphenoxyheptaethylene glycol dipropylene glycol acrylate M-6 : Dimethacrylate of polyethylene glycol with an average of 5 moles of ethylene oxide added to each end of bisphenol A (BPE-500 manufactured by Shin-Nakamura Chemical Co., product name)

M-7: Nonapropylene glycol diacrylate M-8: Nonaethylene glycol diacrylate A-1: 4,4′-bis (diethylamino) benzophenone A-2: 2- (o-chlorophenyl) -4, 5- Diphenylimidazole dimer A-3: 2- (p-methoxytriethoxyphenyl) -4,5-diphenylimidazole dimer (in formula (I), X = methyl group, Y = Z = hydrogen, n1 = 3)
A-4: 2,2 ′, 5-tris (2-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ′, 5′-diphenyl-1,1′-biimidazole B-1: diamond corn -B-2: Leuco Crystal Violet

  The DFR using the photosensitive resin composition of the present invention has excellent sensitivity at the time of exposure, high resolution, little occurrence of scum in the developing process, excellent contrast after exposure, and a peelable piece size. Since it is small and has excellent cured film flexibility, it is useful as a DFR for producing an alkali development type printed wiring board, a lead frame, and a semiconductor package substrate.

Claims (11)

The compound represented by the following general formula (I).

(X is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, Y and Z are each independently selected from the group consisting of a halogen group, a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, and a hydroxyl group. And n ₁ is an integer of ₁ to 10, m ₁ is an integer of ₁ to 5, and m ₂ and m ₃ are each independently an integer of 0 to 5.) (A) Resin for binders comprising a linear polymer having a carboxyl group content of 100 to 600 in terms of acid equivalent and a weight average molecular weight of 5,000 to 500,000 with respect to the entire photosensitive resin composition: 20 -90 mass%, (b) photopolymerizable monomer having at least one terminal ethylenically unsaturated group: 5-75 mass%, (c) photopolymerization initiator: 0.01-30 mass%, c) A photosensitive resin composition containing the following general formula (I) as a photopolymerizable initiator.

(X is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and Y and Z are each independently selected from the group consisting of a halogen group, a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, and a hydroxyl group. And n ₁ is an integer of ₁ to 10, m ₁ is an integer of ₁ to 5, m ₂ and m ₃ are integers of 0 to 5.) The resin for binder (a) contains at least one compound selected from the group represented by the following general formula (II) and general formula (III) as a copolymerization component.
The photosensitive resin composition as described.

(L is a kind of group chosen from the group which consists of a C1-C6 hydrocarbon group or an alkoxy group, a hydroxyl group, and a halogen group, and p is an integer of 0-5.)

(R ₀ is a hydrogen atom or a methyl group, M is a kind of group selected from the group consisting of a hydrocarbon group having 1 to 6 carbon atoms or an alkoxy group, a hydroxyl group, and a halogen group, and q is 0-5. (It is an integer.) (B) at least one compound selected from the group represented by the following general formulas (IV), (V), (VI) and (VII) as a photopolymerizable monomer: 3. The photosensitive resin composition according to 3.

(R ₃ and R ₄ are each independently a hydrogen atom or a methyl group. R ₁ and R ₂ are each an alkylene group having 2 to 6 carbon atoms, which may be the same or different. If they are different, the repeating unit of-(R ₁ -O)-and-(R ₂ -O)-may be a block structure or a random structure, and n ₂ , n _3, n ₄ and n ₅ are 0 or a positive integer, the sum of which is 2-40.)

(R ₇ and R ₈ are each independently a hydrogen atom or a methyl group. R ₅ and R ₆ represent an alkylene group having 2 to ₆ carbon atoms, which may be the same or different. When different, the repeating unit of-(R ₅ -O)-and-(R ₆ -O)-may be a block structure or a random structure, and n ₆ , n _7, n ₈ and n ₉ are 0 Or a positive integer, the sum of which is 2-40.)

(R ₉ and R ₁₀ are each independently a hydrogen atom or a methyl group, and n ₁₀ , n _11, and n ₁₂ are each an integer of 3 to 15)

(R ₁₁ represents a divalent organic group having 4 to 12 carbon atoms, R ₁₂ and R ₁₃ represent hydrogen or a methyl group. A and B are alkylene groups having 2 to 6 carbon atoms, which are the same as each other. In the case where they are different, the repeating unit of-(AO)-and-(BO)-may be a block structure or a random structure, m ₅ , m _6, m _7. And m ₈ is 0 or a positive integer, and the sum of these is 2 to 40.) The photosensitive resin laminated body which provided the photosensitive resin layer which consists of the photosensitive resin composition as described in any one of Claims 2-4 on the support layer. A method for forming a resist pattern, comprising a lamination step of forming a photosensitive resin layer on the substrate using the photosensitive resin laminate according to claim 5, an exposure step, and a development step. The resist pattern forming method according to claim 6, wherein in the exposure step, exposure is performed by direct drawing. The manufacturing method of a printed wiring board including the process of etching or plating the board | substrate which formed the resist pattern by the method of Claim 6 or 7.   A method for manufacturing a lead frame, comprising a step of etching a substrate on which a resist pattern is formed by the method according to claim 6.   A method for manufacturing a semiconductor package, comprising a step of etching or plating a substrate on which a resist pattern is formed by the method according to claim 6.   A method for processing a substrate on which a resist pattern is formed by the method according to claim 6 or 7 by a sandblasting process.